CN108878778A - A kind of preparation method of three-dimensional porous anode plate for lithium ionic cell - Google Patents
A kind of preparation method of three-dimensional porous anode plate for lithium ionic cell Download PDFInfo
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- CN108878778A CN108878778A CN201810628967.2A CN201810628967A CN108878778A CN 108878778 A CN108878778 A CN 108878778A CN 201810628967 A CN201810628967 A CN 201810628967A CN 108878778 A CN108878778 A CN 108878778A
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- copper foil
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of preparation method of three-dimensional porous anode plate for lithium ionic cell, the production for three-dimensional porous lithium battery cathode plate.The present invention leads to porous copper foil roughening process, washing process, three-dimensional porous copper foil surface passivation technology, coating process and is prepared into negative electrode tab coiled strip.The present invention is by porous copper foil before unreeling coating, first design copper foil surface three-dimensional is roughened slot, copper foil surface is subjected to three-dimensional shape little particle tumor, to improve the specific surface area on its surface, increase the contact area with active material, improve mechanical adhesion power, the roughness of copper foil is kept to be basically unchanged simultaneously, in three-dimensional coarsening process, the porous character of copper foil continues to keep, after being further passivated, copper foil surface is directly extracted with squeezing roller, is not dried, and slurry coating link is just directly entered, after the completion of coating, drying, winding process are entered back into.The preparation difficulty for efficiently solving three-dimensional porous anode plate for lithium ionic cell, improves bonding force, by foil three dimensional stress and being made into one of negative electrode tab, can efficiently quick Fabrication negative electrode tab and.
Description
Technical field
The present invention relates to technical field of lithium-ion battery, specifically a kind of three-dimensional porous anode plate for lithium ionic cell
Preparation method.
Background technique
It is universal with lithium ion battery, will be used wider and wider it is general, it is also higher and higher to battery request, especially
New-energy automobile requires power-type lithium ion battery security performance more preferable, and battery capacity is higher, and cycle life is longer.Current each lithium
Ion battery manufacturer is directed to requirements above, constantly researches and develops, or by more effectively utilizing the battery useful space to improve battery
Energy density, or the electro-chemical activity for more fully playing cell active materials are failed very well with improving its effective rate of utilization
Ground meets many requirements of new energy car battery.More preferably to break through above-mentioned bottleneck, industry turns to three-dimensional lithium ion battery one after another
Pole piece carrier foil is carried out three-dimensional porousization, the bonding of foil and active material is improved using three-dimensional foil technology by research
Power.The pole piece of lithium ion battery is three-dimensionality to be mainly reflected on foil, and foil punching processing or corrosion, but porous foil are usually used
It is three-dimensionality and bad, it is not strong to the adhesion strength of active material.If foil is directly pressed into three-dimensional shape, foil winding before coating
It is easy to loosen, winding length is inadequate, and batch micro operations are difficult.Therefore, the manufacture craft of three-dimensional porous lithium battery cathode plate and side
Method is current urgent problem to be solved.
Summary of the invention
In order to overcome the deficiencies of the prior art, it is negative to be to provide a kind of three-dimensional porous lithium ion battery to goal of the invention of the invention
The preparation method of pole piece, to improve the manufacturing quality of three-dimensional porous anode plate for lithium ionic cell.
For achieving the above object, the three-dimensional porous lithium battery cathode plate of the present invention is roughened work by porous copper foil three-dimensional
Skill, washing process, three-dimensional porous copper foil surface passivation technology, coating process are prepared into negative electrode tab coiled strip.
The porous copper foil three-dimensional roughening process step:Porous copper foil makees cathode in three-dimensional slot, opposite in porous copper foil
Anode is installed, centre keeps three-dimensional coarsening solution circulation, it is three-dimensional that electroplating surface is carried out under the action of direct current at the 80mm pole span of face
Roughening；The copper ion concentration of three-dimensional roughening solution is maintained at 15-20g/L in three-dimensional slot, and sulfuric acid concentration is maintained at 90-105g/L,
Solution temperature is maintained at 15-25 DEG C, and liquid inventory is maintained at 0.5-5m3/ h, current density 80-120A/dm2, porous copper foil speed
Degree is 4-8m/min；When roughening, there is acid mist to emerge, needs acid adding mist blower unit.
The washing process step：It is provided with spray tube in rinse bath, is equipped with ten to 14 on every spray tube
Two spray tubes up and down are respectively arranged on three-dimensional porous copper foil two sides in the atomizer of 2-5L/min, and after the completion of hydro-peening, spray washing is straight
Run in into sewage treatment equipment；Spray washing uses deionization pure water, and water temperature is maintained at 20-30 DEG C, pressure of supply water 2-3kgf, and three
Dimension porous copper foil speed is 4-8m/min.
The three-dimensional porous copper foil surface passivation technology step：Three-dimensional porous copper foil makees cathode in deactivation slot, opposite at it
Anode is installed, centre keeps passivating solution circulation, electroplating surface passivation is carried out under the action of direct current at the 80mm pole span of face；Passivation
In slot passivating solution phosphorus acid content be 0.5-1g/L, chromium trioxide content be 0.7-1.2g/L, zinc sulfate content 1.3-2.5g/L,
Current density is maintained at 10-50A/dm2, passivation flow quantity is 1-5 m3/ h, temperature are maintained at 20-30 DEG C, three-dimensional porous copper foil speed
Degree is 4-8m/min；Suddenly enter spray washing device after the completion of passivation, carry out water in rinse bath by above-mentioned washing process step
It washes.
The coating process step：By three-dimensional porous copper foil is two-sided while extrusion coating negative electrode slurry, coater oven temperature
Degree is maintained at 90 DEG C -150 DEG C, and three-dimensional porous copper foil walking speed is 4-8m/min, is prepared into anode plate for lithium ionic cell, and coiled
Shape negative electrode tab.
Compared with prior art, the present invention first design copper foil surface three-dimensional by porous copper foil before unreeling coating and be roughened slot,
Copper foil surface is subjected to three-dimensional shape little particle tumor, to improve the specific surface area on its surface, increases the contact surface with active material
Product improves mechanical adhesion power, while the roughness of copper foil being kept to be basically unchanged, in three-dimensional coarsening process, the porous spy of copper foil
Sign continues to keep, and after being further passivated, copper foil surface is directly extracted with squeezing roller, is not dried, and is just directly entered slurry coating
Link after the completion of coating, enters back into drying, winding process.Efficiently solve the preparation of three-dimensional porous anode plate for lithium ionic cell
Difficulty improves bonding force, by foil three dimensional stress and being made into one of negative electrode tab, can efficiently quick Fabrication negative electrode tab and
It can consumption reduction.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is negative electrode tab thickness distribution map of the invention.
Fig. 3 is surface density distribution map of the invention.
Specific embodiment
As shown in Figure 1, three-dimensional porous lithium battery cathode plate of the invention passes through porous copper foil three-dimensional roughening process, washing work
Skill, three-dimensional porous copper foil surface passivation technology, coating process are prepared into negative electrode tab coiled strip.
Porous copper foil surface will be roughened, and solution compolision plays a crucial role.Porous copper foil three-dimensional roughening process step of the invention
Suddenly:Porous copper foil makees cathode in three-dimensional slot, and anode is installed at porous copper foil opposite face 80mm pole span, and centre keeps three-dimensional
Coarsening solution circulation, carries out the roughening of electroplating surface three-dimensional under the action of direct current；The copper ion of three-dimensional roughening solution in three-dimensional slot
Concentration is maintained at 15-20g/L, and sulfuric acid concentration is maintained at 90-105g/L, and solution temperature is maintained at 15-25 DEG C, and liquid inventory is kept
In 0.5-5m3/ h, current density 80-120A/dm2, porous copper foil speed is 4-8m/min；When roughening, there is acid mist to emerge, needs
Want acid adding mist blower unit.
After the completion of the roughening of porous copper foil three-dimensional, surface can remain three-dimensional roughening electrolyte and need to prevent from influencing passivation effect
The electrolyte of copper foil surface is cleaned.Washing process step of the invention：It is provided with spray tube in rinse bath, every
The atomizer of ten to 14 2-5L/min is housed on spray tube, two sprays up and down are respectively set on three-dimensional porous copper foil two sides
It manages, after the completion of hydro-peening, spray washing is directly discharged into sewage treatment equipment；Spray washing uses deionization pure water, and water temperature is maintained at 20-30
DEG C, pressure of supply water 2-3kgf, three-dimensional porous copper foil speed is 4-8m/min.
Copper foil will prevent from being oxidized in coating sizing-agent high temperature drying process, therefore do surface passivating treatment.The present invention
Copper foil surface passivation technology step：Copper foil makees cathode in deactivation slot, installs anode in the place of copper foil opposite face about 80mm,
Centre keeps passivating solution circulation, and electroplating surface passivation is carried out under the action of direct current；Passivating solution passivation technology phosphorus in deactivation slot
Acid content is 0.5-1g/L, and chromium trioxide content is 0.7-1.2g/L, zinc sulfate content 1.3-2.5g/L, current density holding
In 10-50A/dm2, passivation flow quantity is 1-5 m3/ h, temperature are maintained at 20-30 DEG C；Suddenly enter spray washing after the completion of passivation to fill
It sets, is washed in rinse bath by above-mentioned washing process step.
Coating process step of the invention：By three-dimensional porous copper foil is two-sided while extrusion coating negative electrode slurry, coater oven
Temperature is maintained at 90 DEG C -150 DEG C, walking speed 4-8m/min, is prepared into qualified lithium battery cathode plate, and harvest web-like negative electrode tab.
Example one
Using 8 um porous dual light copper foils, 100 microns of aperture, porosity 17%, copper foil speed 4m/min.
1）Three-dimensional roughening process parameter：Copper ion concentration is maintained at 17g/L, and sulfuric acid concentration is maintained at 100g/L, solution temperature
Degree is maintained at 18-22 DEG C, and liquid inventory is maintained at 1m3/ h, current density keep 90A/dm2。
2）Washing process parameter：Using 10 spray heads, spray head pressure of supply water is 2kgf, flow 5L/H, and water temperature is maintained at 20
℃-30℃。
3）Passivation technology parameter：Phosphorus acid content 0.65g/L, chromium trioxide 0.8g/L, zinc sulfate content 1.3g/L, electric current are close
Degree is maintained at 20A/dm2, it is passivated 2 m of flow quantity3/ h, 20-22 DEG C of temperature.Washing uses 10 spray heads, and spray head pressure of supply water is
2kgf, flow 5L/H, water temperature are maintained at 20 DEG C -30 DEG C.
4）Coating process parameter：It is porous foil is two-sided while applying negative electrode slurry, 90 DEG C of coater oven temperature, walking speed
4m/min is prepared into qualified lithium battery cathode plate, and the negative electrode tab of harvest web-like.
Example two
Using 9 um porous dual light copper foils, 95 microns of aperture, porosity 20%, copper foil speed 6m/min.
1）Three-dimensional roughening process parameter：Copper ion concentration is maintained at 19g/L, and sulfuric acid concentration is maintained at 100g/L, solution temperature
Degree is maintained at 18-22 DEG C, and liquid inventory is maintained at 2m3/ h, current density keep 100A/dm2。
2）Washing process parameter：Using 12 spray heads, spray head pressure of supply water is 2.5kgf, flow 3L/H, and water temperature is maintained at
20℃-30℃。
3）Passivation technology parameter：Phosphorus acid content 0.7g/L, chromium trioxide 0.9g/L, zinc sulfate content 1.6g/L, electric current are close
Degree is maintained at 25A/dm2, it is passivated 2 m of flow quantity3/ h, 20-22 DEG C of temperature.Washing uses 12 spray heads, each spray head pressure of supply water
For 2.5kgf, flow 3L/H, water temperature is maintained at 20 DEG C -30 DEG C.
4）Coating process parameter：It is porous foil is two-sided while applying negative electrode slurry, 120 DEG C of coater oven temperature, walking speed
6m/min is prepared into qualified lithium battery cathode plate, and the negative electrode tab of harvest web-like.
Example three
Using 12 um porous dual light copper foils, 95 microns of aperture, porosity 25%, copper foil speed 8m/min.
1）Three-dimensional roughening process parameter：Copper ion concentration is maintained at 20g/L, and sulfuric acid concentration is maintained at 105g/L, solution temperature
Degree is maintained at 20-25 DEG C, and liquid inventory is maintained at 2m3/ h, current density keep 120A/dm2。
2）Washing process parameter：Using 14 spray heads, spray head pressure of supply water is 3kgf, flow 2L/H, and water temperature is maintained at 20
℃-30℃。
3）Passivation technology parameter：Phosphorus acid content 0.7g/L, chromium trioxide 1.1g/L, zinc sulfate content 2g/L, current density
It is maintained at 30A/dm2, it is passivated 2 m of flow quantity3/ h, 20-22 DEG C of temperature.Washing process parameter：Using 14 spray heads, spray head supplies water
Pressure is 3kgf, flow 2L/H, and water temperature is maintained at 20 DEG C -30 DEG C.
4）Painting parameter：It is porous foil is two-sided while applying negative electrode slurry, 150 DEG C of coater oven temperature, walking speed 8m/
Min is prepared into qualified lithium battery cathode plate, and the negative electrode tab of harvest web-like.
After the present invention is coated according to the negative electrode tab that above method produces, the thickness of pole piece can satisfy production, technique
It is required that the thickness range of measurement is relatively concentrated, consistency is preferable, and specific data distribution is as shown in Fig. 2, relative to common foil
The thickness of the negative electrode tab of material preparation, the thickness distribution narrow range of negative electrode tab made of three-dimensional foil, uniformity are high.
The present invention is sampled measurement data to the surface density of pole piece and analyzes simultaneously, and the surface density of pole piece compares
Compared with concentration, there is preferable consistency, pole piece is good without bad phenomenons, appearances such as apparent particle, thin, the slurry accumulations of dew.
Surface density distribution is as shown in figure 3, the surface density of the negative electrode tab pole piece of three-dimensional foil preparation is evenly distributed relative to common foil, number
According to favorable reproducibility.
Claims (5)
1. a kind of preparation method of three-dimensional porous anode plate for lithium ionic cell, it is characterised in that：The three-dimensional porous lithium battery is negative
Pole piece is prepared by porous copper foil three-dimensional roughening process, washing process, three-dimensional porous copper foil surface passivation technology, coating process
Negative electrode tab coiled strip.
2. a kind of preparation method of three-dimensional porous anode plate for lithium ionic cell according to claim 1, it is characterised in that：Institute
State porous copper foil three-dimensional roughening process step:Porous copper foil makees cathode in three-dimensional slot, in porous copper foil opposite face 80mm pole span
Place's installation anode, centre keep three-dimensional coarsening solution circulation, the roughening of electroplating surface three-dimensional are carried out under the action of direct current；Three-dimensional slot
The copper ion concentration of middle three-dimensional roughening solution is maintained at 15-20g/L, and sulfuric acid concentration is maintained at 90-105g/L, and solution temperature is kept
At 15-25 DEG C, liquid inventory is maintained at 0.5-5m3/ h, current density 80-120A/dm2, porous copper foil speed is 4-8m/
min；When roughening, there is acid mist to emerge, needs acid adding mist blower unit.
3. a kind of preparation method of three-dimensional porous anode plate for lithium ionic cell according to claim 1, it is characterised in that：Institute
The washing process step stated：It is provided with spray tube in rinse bath, is equipped with ten to 14 2-5L/min's on every spray tube
Two spray tubes up and down are respectively arranged on three-dimensional porous copper foil two sides in atomizer, and after the completion of hydro-peening, spray washing is directly discharged into waste water
Processing equipment；Spray washing uses deionization pure water, and water temperature is maintained at 20-30 DEG C, pressure of supply water 2-3kgf, three-dimensional porous copper foil
Speed is 4-8m/min.
4. a kind of preparation method of three-dimensional porous anode plate for lithium ionic cell according to claim 1, it is characterised in that：Institute
The three-dimensional porous copper foil surface passivation technology step stated：Three-dimensional porous copper foil makees cathode in deactivation slot, in its opposite face 80mm
Anode is installed, centre keeps passivating solution circulation, electroplating surface passivation is carried out under the action of direct current at pole span；It is blunt in deactivation slot
Change liquid phosphorus acid content is 0.5-1g/L, and chromium trioxide content is 0.7-1.2g/L, zinc sulfate content 1.3-2.5g/L, and electric current is close
Degree is maintained at 10-50A/dm2, passivation flow quantity is 1-5 m3/ h, temperature are maintained at 20-30 DEG C, and three-dimensional porous copper foil speed is 4-
8m/min；Suddenly enter spray washing device after the completion of passivation, washed in rinse bath by above-mentioned washing process step.
5. a kind of preparation method of three-dimensional porous anode plate for lithium ionic cell according to claim 1, it is characterised in that：Institute
The coating process step stated：It is three-dimensional porous copper foil is two-sided while extrusion coating negative electrode slurry, coater oven temperature are maintained at 90
DEG C -150 DEG C, three-dimensional porous copper foil walking speed is 4-8m/min, is prepared into anode plate for lithium ionic cell, and harvest web-like negative electrode tab.
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| CN201810628967.2A CN108878778A (en) | 2018-06-19 | 2018-06-19 | A kind of preparation method of three-dimensional porous anode plate for lithium ionic cell |
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| CN201810628967.2A CN108878778A (en) | 2018-06-19 | 2018-06-19 | A kind of preparation method of three-dimensional porous anode plate for lithium ionic cell |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554738A (en) * | 2018-12-19 | 2019-04-02 | 胡旭日 | A kind of negative electrode of lithium ion battery copper foil production equipment and method |
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Application publication date: 20181123 |